A tetrakis(fluoroaryl)borate derivative is an useful compound as, for example, a co-catalyst for promoting the activity of a metallocene catalyst (polymeric catalyst) used in a cationic complex polymerization reaction, or a photopolymeric catalyst for silicone. Also, tetrakis(fluoroaryl)borate.magnesium halide is an useful compound as an intermediate for producing the tetrakis(fluoroaryl)borate derivative. Recently, the metallocene catalyst has been receiving considerable attention as a polyolefin polymeric catalyst.
A producing process of tetrakis (pentafluorophenyl)borate.magnesium bromide, which is a kind of tetrakis(fluoroaryl)borate.magnesium halide, from bromopentafluorobenzene through the Grignard reaction is disclosed in, for example, Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980).
Also, in Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981), a process of synthesizing tetrakis(pentafluorophenyl)borate.lithium from pentafluorobenzene using an organic lithium compound and boron halide first, and thence reacting the resulting compound with N,N-dimethylaniline.hydrochloride is disclosed as a producing process of a tetrakis(pentafluorophenyl)borate derivative, which is a kind of the tetrakis(fluoroaryl)borate derivative.
Further, a producing process of the tetrakis(pentafluorophenyl)borate derivative by reacting tetrakis(pentafluorophenyl)borate.magnesium bromide with N,N-dimethylaniline.hydrochloride is disclosed in U.S. Pat. No. 5,473,036.
However, Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) neither discloses nor implies the separation/removal of magnesium halide, a by-product produced with tetrakis(pentafluorophenyl)borate.magnesium bromide, from the reaction series. If the tetrakis(pentafluorophenyl)borate derivative is produced from tetrakis(pentafluorophenyl)borate.magnesium bromide containing magnesium halide as impurities, and used as a co-catalyst of the metallocene catalyst, for example, the activity of the metallocene catalyst deteriorates considerably. The process disclosed in Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) is a producing process of tetrakis(pentafluorophenyl)borate.magnesium bromide containing magnesium halide as impurities. Thus, tetrakis(pentafluorophenyl)borate.magnesium bromide obtained through this process can not be used as an adequate intermediate for producing the tetrakis(pentafluorophenyl)borate derivative.
If typical alkali treatment is applied to tetrakis(pentafluorophenyl)borate.magnesium bromide to remove magnesium halide from tetrakis(pentaflurorphenyl)borate.magnesium bromide obtained by the process disclosed in the above publication, magnesium hydroxide is produced. Since magnesium hydroxide turns a post-treatment solution into gel, the solution can not be filtered. In other words, since magnesium halide can not be removed by the typical alkali treatment, it is difficult to separate tetrakis(pentafluorophenyl)borate.magnesium bromide obtained in the above process, or to obtain a highly-pure tetrakis(fluoroaryl)borate compound after the treatment.
Thus, there has been an increasing demand for a purifying process for separating/removing impurities, such as magnesium halide, from tetrakis(fluoroaryl)borate.magnesium halide readily and efficiently.
On the other hand, the process disclosed in Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) has the following problems:
(1) since the reaction series must be kept at -65.degree. C. or below, not only special equipment is required, but also the cooling cost is high; PA1 (2) the process demands an expensive organic lithium compound (t-butyl lithium), which is a dangerous compound because it may ignite when reacted with water and the like; PA1 (3) the process also demands expensive boron halide (boron trichloride), which is very difficult to handle because it is in the gaseous state and corrosive. Thus, the process disclosed in the above publication can not be readily adopted for industrial use. PA1 the impurities, such as magnesium halide, can be readily and efficiently separated/removed from tetrakis(fluoroaryl)borate.magnesium halide by treating tetrakis(fluoroaryl)borate.magnesium halide with, for example, alkali metal salts of carboxylic acid and/or alkali earth metal salts of carboxylic acid; and PA1 an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative, which is useful as, for example, a co-catalyst of the metallocene catalyst or a photopolymeric catalyst for silicone, can be produced efficiently by reacting a tetrakis(fluoroaryl)borate compound obtained through the above purifying process with a compound generating monovalent cationic seeds. PA1 1 alkali metal salts of carboxylic acid and/or alkali earth metal salts of carboxylic acid; PA1 2 an acid; PA1 3 an acid followed by alkali metal hydroxide and/or alkaline earth metal hydroxide; or PA1 4 an acid followed by alkali metal salts of carboxylic acid and/or alkaline earth metal salts of carboxylic acid. PA1 with an ether compound expressed by General Formula (6): EQU R.sub.11 --O--Y--O--R.sub.12 (6) PA1 where each of R.sub.11 and R.sub.12 represents a hydrocarbon group which may include a substituent group containing a hetero atom, and Y represents a hydrocarbon bivalent group. PA1 1 alkali metal salts of carboxylic acid and/or alkali earth metal salts of carboxylic acid; PA1 2 an acid; PA1 3 an acid followed by alkali metal hydroxide and/or alkaline earth metal hydroxide; or PA1 4 an acid followed by alkali metal salts of carboxylic acid and/or alkaline earth metal salts of carboxylic acid. PA1 ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole; PA1 aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane; PA1 alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane; PA1 aromatic hydrocarbon solvents, such as benzene and toluene; etc. PA1 alkali metal salts of saturated aliphatic monocarboxylic acid, such as sodium formate, potassium formate, sodium acetate, potassium acetate, sodium propionate, and potassium propionate; PA1 mono- or dialkali metal salts of saturated aliphatic dicarboxylic acid, such as sodium oxalate monobasic, sodium oxalate dibasic, potassium oxalate monobasic, potassium oxalate dibasic, sodium malonate monobasic, sodium malonate dibasic, potassium malonate monobasic, potassium malonate dibasic, sodium succinate monobasic, sodium succinate dibasic, potassium succinate monobasic, and potassium succinate dibasic; PA1 alkali metal salts of unsaturated aliphatic monocarboxylic acid, such as sodium acrylate, potassium acrylate, sodium methacrylate, and potassium methacrylate; PA1 mono- or dialkali metal salts of unsaturated aliphatic dicarboxylic acid, such as sodium maleate monobasic, sodium maleate dibasic, potassium maleate monobasic, potassium maleate dibasic, sodium fumarate monobasic, sodium fumarate dibasic, potassium fumarate monobasic, and potassium fumarate dibasic; PA1 alkali metal salts of aromatic monocarboxylic acid, such as sodium benzoate and potassium benzoate; PA1 mono- or dialkali metal salts of aromatic dicarboxylic acid, such as sodium phthalate monobasic, sodium phthalate dibasic, potassium phthalate monobasic, potassium phthalate dibasic, sodium isophthalate monobasic, sodium isophthalate dibasic, potassium isophthalate monobasic, potassium isophthalate dibasic, sodium terephthalate monobasic, sodium terephthalate dibasic, potassium terephthalate monobasic, and potassium terephthalate dibasic; etc. PA1 alkaline earth metal salts of saturated aliphatic monocarboxylic acid, such as calcium formate, barium formate, calcium acetate, barium acetate, calcium propionate, and barium propionate; PA1 alkaline earth metal salts of saturated aliphatic dicarboxylic acid, such as calcium oxalate, barium oxalate, calcium malonate, barium malonate, calcium succinate, and barium succinate; PA1 alkaline earth metal salts of unsaturated aliphatic monocarboxylic acid, such as calcium acrylate, barium acrylate, calcium methacrylate, and barium methacrylate; PA1 alkaline earth metal salts of unsaturated aliphatic dicarboxylic acid, such as calcium maleate, barium maleate, calcium fumarate, and barium fumarate; PA1 alkaline earth metal salts of aromatic monocarboxylic acid, such as calcium benzoate and barium benzoate; PA1 alkaline earth metal salts of aromatic dicarboxylic acid, such as calcium phthalate, barium phthalate, calcium isophthalate, barium isophthalate, calcium terephthalate, and barium terephthalate; etc. In the present invention, the alkaline earth metal salts of carboxylic acid include carbonates, such as calcium carbonate and barium carbonate. Note that, however, in the present invention, the alkaline earth metal salts of carboxylic acid do not include magnesium salts of carboxylic acid. PA1 inorganic acids, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid; PA1 organic acids, such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, and succinic acid; etc. PA1 water; PA1 ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole; PA1 aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane; PA1 alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane; PA1 ester solvents, such as methyl acetate and ethyl acetate; PA1 aromatic hydrocarbon solvents, such as benzene and toluene; treating tetrakis(fluoroaryl)borate.magnesium halide with the acid followed by the hydroxide or carboxylate is not especially limited. For example, the acid can be readily separated from a solution of the tetrakis(fluoroaryl)borate compound by a simple manipulation, such as liquid separation (oil-water separation). After the treatment, the tetrakis(fluoroaryl)borate compound is obtained in the form of a solution dissolved into the solvent. PA1 alcohol solvents, such as methyl alcohol and ethyl alcohol; PA1 ketone solvents, such as acetone and methyl ethyl ketone; etc. PA1 1 a process of treating tetrakis(fluoroaryl)borate.magnesium halide with carboxylate; PA1 2 a process of treating tetrakis(fluoroaryl)borate.magnesium halide with an acid; PA1 3 a process of treating tetrakis(fluoroaryl)borate.magnesium halide with an acid followed by the hydroxide; and PA1 4 a process of treating tetrakis(fluoroaryl)borate.magnesium halide with an acid followed by the carboxylate. PA1 ammonium cations, such as n-butyl ammonium, dimethyl ammonium, trimethyl ammonium, triethyl ammonium, triisopropyl ammonium, tri-n-butyl ammonium, tetramethyl ammonium, tetraethyl ammonium, and tetra-n-butyl ammonium; PA1 anilinium cations, such as anilinium, N-methyl anilinium, N,N-dimethyl anilinium, N,N-diethyl anilinium, N,N-diphenyl anilinium, and N,N,N-trimethyl anilinium; PA1 pyridinium cations, such as pyridinium, N-methyl pyridinium, and N-benzyl pyridinium; PA1 quinolinium cations, such as quinolinium and isoquinolinium; PA1 phosphonium cations, such as dimethylphenyl phosphonium, triphenyl phosphonium, tetraethyl phosphonium, and tetraphenyl phosphonium; PA1 sulfonium cations, such as trimethyl sulfonium and triphenyl sulfonium; PA1 iodonium cations, such as diphenyl iodonium and di-4-methoxy phenyl iodonium; PA1 carbenium cations, such as triphenyl carbenium and tri-4-methoxyphenyl carbenium; PA1 monovalent cations of metals other than alkali metal and alkali earth metal; etc. PA1 quaternary ammonium compounds, such as tri-n-butylamine.hydrochloride, N,N-dimethylaniline.hydrochloride, N,N-dimethylaniline.sulfate, and tetramethyl ammonium chloride; PA1 nitrogen-containing aromatic heterocyclic compounds, such as pyridine hydrochloride, quinoline.hydrochloride, N-methyl pyridine iodide, and N-methyl quinoline iodide; PA1 quaternary phosphonium compounds, such as n-butylphosphonium bromide and tetraphenyl phosphonium bromide; PA1 sulfonium compounds, such as trimethyl sulfonium iodide; PA1 iodinium compounds, such as diphenyl iodinium chloride; PA1 carbenium compounds, such as trityl chloride; etc. PA1 water; PA1 ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole; PA1 aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane; PA1 alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane; PA1 ester solvents, such as methyl acetate and ethyl acetate; PA1 aromatic hydrocarbon solvents, such as benzene and toluene; PA1 alcohol solvents, such as methyl alcohol and ethyl alcohol; PA1 ketone solvents, such as acetone and methyl ethyl ketone; etc. PA1 a method of mixing the tetrakis(fluoroaryl)borate compound and cation seed generating compound with the reaction solvent; PA1 a method of mixing the cation seed generating compound or a solution thereof with a solution of the tetrakis(fluoroaryl)borate compound; PA1 a method of mixing the tetrakis(fluoroaryl)borate compound or a solution thereof with a solution of the cation seed generating compound; etc. PA1 substituents containing oxygen atoms, such as an alkoxy group, an aryloxy group, a cycloalkyloxy group, and an acyloxy group; PA1 substituents containing nitrogen atoms, such as a dialkyl amino group; PA1 substituents containing sulfur atoms, such as an alkylthio group and an arylthio group; etc. PA1 The hydrocarbon bivalent group is preferably a bivalent group selected from the group consisting of an alkylene group having up to six carbon atoms as a carbon chain linking two oxygen atoms, namely, a methylene group possibly having a substituent, an ethylene group possibly having a substituent, a trimethylene group possibly having a substituent, a tetramethylene group possibly having a substituent, a pentamethylene group possibly having a substituent, and a hexamethylene group possibly having a substituent. It is more preferable that the substituent in the bivalent group is an alkyl group having up to six carbon atoms. PA1 ethylene glycol dialkyl ether, such as 1,2-dimethoxy ethane, 1,2-diethoxy ethane, ethylene glycol di-n-propyl ether, ethylene glycol diisopropyl ether, ethylene glycol di-n-butyl ether, ethylene glycol diisobutyl ether, ethylene glycol di-sec-butyl ether, ethylene glycol di-t-butyl ether, ethylene glycol dipentyl ether, ethylene glycol dineopentyl ether, ethylene glycol dihexyl ether, ethylene glycol diheptyl ether, ethylene glycol dioctyl ether, ethylene glycol dinonyl ether, and ethylene glycol didecyl ether; PA1 ethylene glycol dicycloalkyl ether, such as ethylene glycol dicyclopropyl ether, ethylene glycol dicyclo butyl ether, ethylene glycol dicyclopentyl ether, ethylene glycol dicyclohexyl ether, ethylene glycol diheptyl ether, ethylene glycol dicyclo octyl ether, ethylene glycol dicyclo nonyl ether, and ethylene glycol dicyclo decyl ether; PA1 unsymetric ethylene glycol methyl alkyl ether, such as ethylene glycol methyl ethyl ether, ethylene glycol methyl isopropyl ether, and ethylene glycol methyl butyl ether; PA1 diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diisopropyl ether, diethylene glycol dibutyl ether, diethylene glycol dipentyl ether, diethylene glycol dihexyl ether, diethylene glycol diheptyl ether, diethylene glycol dioctyl ether, diethylene glycol dinonyl ether, and diethylene glycol didecyl ether; PA1 triethylene glycol dialkyl ether, such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol diisopropyl ether, triethylene glycol dibutyl ether, triethylene glycol dipentyl ether, triethylene glycol dihexyl ether, triethylene glycol diheptyl ether, triethylene glycol dioctyl ether, triethylene glycol dinonyl ether, and triethylene glycol didecyl ether; PA1 ethylene glycol dialkyl ether having an acyloxy group, such as diethylene glycol monoethyl ether acetate and diethylene glycol monoethyl ether methacrylate; PA1 ethylene glycol dialkyl ether having an alkylthio group, such as ethylene glycol di-2-methylthio ethyl ether; PA1 ethylene glycol dialkyl ether having a dialkyl amino group, such as ethylene glycol di-2-dimethyl amino ethyl ether; PA1 ethylene glycol diaryl ether, such as ethylene glycol diphenyl ether; PA1 diethylene glycol diaryl ether, such as diethylene glycol diphenyl ether; PA1 triethylene glycol diaryl ether, such as triethylene glycol diphenyl ether; PA1 ethylene glycol dibenzyl ether; etc. PA1 ether solvents, such as diethyl ether, diisopropyl ether, dibutyl ether, and anisole; PA1 aliphatic hydrocarbon solvents, such as pentane, hexane, and heptane; PA1 alicyclic hydrocarbon solvents, such as cyclopentane and cyclohexane; PA1 ester solvents, such as methyl acetate and ethyl acetate; PA1 aromatic hydrocarbon solvents, such as benzene and toluene; etc. PA1 a first producing process, in which, after tetrakis(fluoroaryl)borate is obtained by removing the polyfunctional ether from the tetrakis(fluoroaryl)borate ether complex, the resulting tetrakis(fluoroaryl)borate is reacted with the cation seed generating compound; PA1 a second producing process, in which, after the tetrakis(fluoroaryl)borate derivative.ether complex is obtained by reacting the tetrakis(fluoroaryl)borate ether complex with the cation seed generating compound, the polyfunctional ether is removed from the resulting tetrakis(fluoroaryl)borate derivative.ether complex.
In the process disclosed in U.S. Pat. No. 5,473,036, magnesium hydroxide is produced as a by-product with the object product, that is, the tetrakis(pentafluorophenyl)borate derivative. Since magnesium hydroxide turns a post-treatment solution into gel, it is difficult to separate (isolate) the tetrakis(pentafluorophenyl)borate derivative from the solution. Thus, there arises a problem that the tetrakis(pentafluorophenyl)borate derivative can not be produced efficiently.
In other words, the conventional producing processes have a problem that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can not be produced efficiently. Hence, there has been an increasing demand for a process of producing an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative efficiently.
Therefore, it is a first object of the present invention to provide a purifying process of separating/removing impurities, such as magnesium halide, from tetrakis(fluoroaryl)borate.magnesium halide readily and efficiently. Also, it is a second object of the present invention to provide a process of efficiently producing an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative, which is useful as, for example, a co-catalyst of the metallocene catalyst or a photopolymeric catalyst for silicone.
A producing process of tetrakis(pentafluorophenyl)borate, which is useful as an intermediate for producing the tetrakis(pentafluorophenyl)borate derivatives of various kinds, has been known.
For example, a process of obtaining tetrakis(pentafluorophenyl)borate.lithium by reacting pentafluorophenyl lithium, which is produced by reacting pentafluorophenyl bromide with butyl lithium at -78.degree. C. in dry pentane, with tris(pentafluorophenyl)borate at -78.degree. C. in dry pentane is disclosed in p245, J. Organometallic. Chem., 2, (1964).
Also, aforementioned Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) discloses a preparing process of tetrakis(pentafluorophenyl)borate.lithium used in the producing process of N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate from N,N-dimethylaniline.hydrochloride as follows.
That is, the above publication discloses a preparing process, in which pentafluorophenyl lithium is produced initially by reacting pentafluorophenyl bromide with t-butyl lithium at -65.degree. C. in dry diethyl ether, and then tetrakis(pentafluorophenyl)borate.lithium is prepared by reacting the resulting pentafluorophenyl lithium with boron trichloride at -65.degree. C. to -55.degree. C. in dry pentane.
However, the process disclosed in p245, J. Organometallic. Chem., 2, (1964) has a problem that the yield of tetrakis(pentafluorophenyl)borate.lithium is low (43%). Also, since the process disclosed in aforementioned Japanese Laid-open Patent Application No. 247981/1994 (Tokukaihei No. 6-247981) has the above-explained problem, it can not be readily applied to industrial use.
On the other hand, aforementioned Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980) discloses a process of obtaining the tetrakis(pentafluorophenyl)borate derivative by reacting pentafluorophenyl magnesium bromide, which is a Grignard reagent, with a boron trifluoride.diethyl ether complex.
Also, aforementioned U.S. Pat. No. 5,473,036 discloses a process of obtaining tetrakis(pentafluorophenyl)borate.magnesium bromide by reacting pentafluorophenyl magnesium bromide, which is a Grignard reagent, with a boron trifluoride.diethyl ether complex, and a process of obtaining N,N-dimethyl anilinium.tetrakis(pentafluorophenyl)borate by reacting tetrakis(pentafluorophenyl)borate.magnesium bromide with an aqueous solution of N,N-dimethylaniline.hydrochloride.
However, in the process disclosed in Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980), magnesium halide, such as magnesium bromide fluoride (MgBrF), produced as a by-product with tetrakis(pentafluorophenyl)borate.magnesium bromide, is not separated/removed from the reaction series and remains therein as impurities. Thus, as previously mentioned, if the tetrakis(pentafluorophenyl)borate derivative is produced from tetrakis(pentafluorophenyl)borate.magnesium bromide containing magnesium halide as impurities and used as a co-catalyst of the metallocene catalyst, for example, the activity of the metallocene catalyst deteriorates considerably.
Further, in the processes disclosed in U.S. Pat. No. 398,236 and Japanese Laid-open Patent Application No. 247980/1994 (Tokukaihei No. 6-247980), resulting tetrakis(pentafluorophenyl)borate.magnesium bromide is colored with a coloring component derived from the Grignard reaction. Thus, if the tetrakis(pentafluorophenyl)borate derivative is produced from tetrakis(pentafluorophenyl)borate.magnesium bromide obtained in either of the above processes, there arises a problem that the coloring component remains in the tetrakis(pentafluorophenyl)borate derivative (the tetrakis(pentafluorophenyl)borate derivative is colored).
The producing process of tetrakis(pentafluorophenyl)borate derivative disclosed in U.S. Pat. No. 5,473,036 also has the following problem. That is, in the above process, a post-treatment solution is turned into gel by magnesium hydroxide produced as a by-product. Thus, it is difficult to filter the solution and isolate the tetrakis(pentafluorophenyl)borate derivative from the solution. Also, to isolate the tetrakis(pentafluorophenyl)borate derivative in the above process, a crude product must be crystallized again using a chlorine solvent, such as chloroform and dichloroethane.
As has been explained, since tetrakis(fluoroaryl)borate.magnesium bromide obtained by the conventional processes contains the by-product salts and coloring component as impurities, it can not be used as an adequate intermediate for producing the tetrakis(fluoroaryl)borate derivative. Hence, there has been an increasing demand for a tetrakis(fluoroaryl)borate derivative which can be used as a suitable intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds.
It is therefore a third object of the present invention to provide a tetrakis(fluoroaryl)borate ether complex as a new material which can be used suitably as a co-catalyst of the metallocene catalyst, a cationic polymerization initiator, an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds and the like, and a producing process of the same.
Also, the conventional producing processes of the tetrakis(fluoroaryl)borate derivative from tetrakis(fluoroaryl)borate prepared using an organic lithium compound or a Grignard reagent has a problem that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can not be produced efficiently.
It is therefore a fourth object of the present invention to provide a producing process of an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative efficiently. Also, it is a fifth object of the present invention to provide a producing process of highly-pure tetrakis(fluoroaryl)borate. Further, it is a sixth object of the present invention to provide a tetrakis(fluoroaryl)borate derivative.ether complex as a new material, which is useful not only as an intermediate for producing the tetrakis(fluoroaryl)borate derivative, but also as a co-catalyst of the metallocene catalyst (polymeric catalyst) used in the cationic complex polymerization reaction, and a producing process of the same. Furthermore, it is a seventh object of the present invention to provide a producing process of an inexpensive tetrakis(fluoroaryl)borate derivative from the tetrakis(fluoroaryl)borate derivative.ether complex efficiently.
To fulfill the first and second objects, the inventors of the present invention conducted an assiduous study on the purifying process of tetrakis(fluoroaryl)borate.magnesium halide and the producing process of the tetrakis(fluoroaryl)borate derivative. In due course, the inventors achieved the present invention when they discovered that:
In other words, to fulfill the above objects, a purifying process of tetrakis(fluoroaryl)borate.magnesium halide of the present invention is characterized by treating tetrakis(fluoraryl)borate.magnesium halide expressed by General Formula (1): ##STR2##
where each of R.sub.1 -R.sub.10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R.sub.1 -R.sub.5 represents a fluorine atom and at least one of R.sub.6 -R.sub.10 represents a fluorine atom, X represents a chlorine atom, a bromine atom, or an iodide atom, and n represents 2 or 3, with:
According to the above process, magnesium halide, such as magnesium bromide fluoride, produced as a by-product during the producing process of tetrakis(fluoroaryl)borate.magnesium halide through the Grignard reaction can be turned into water-soluble or water-insoluble magnesium salts (that is, in the state of salts other than magnesium hydroxide). Thus, the salts can be readily and efficiently separated/removed from tetrakis(fluoroaryl)borate.magnesium halide through oil-water separation, filtration or the like. In short, the impurities, such as magnesium halide, can be readily and efficiently separated/removed from tetrakis(fluoroaryl)borate.magnesium halide.
When tetrakis(fluoroaryl)borate.magnesium halide is treated with the purifying process 1, 3 or 4, alkali metal salts and/or alkali earth metal salts of tetrakis(fluoroaryl)borate can be obtained. When tetrakis(fluoroaryl)borate.magnesium halide is treated with the purifying process 2, hydrogen compound of tetrakis(fluoroaryl)borate can be obtained.
A producing process of a tetrakis(fluoroaryl)borate derivative of the present invention relates to a producing process of a tetrakis(fluoroaryl)borate derivative expressed by General Formula (2): ##STR3##
where each of R.sub.1 -R.sub.10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R.sub.1 -R.sub.5 represents a fluorine atom and at least one of R.sub.6 -R.sub.10 represents a fluorine atom, Z.sup.+ represents a monovalent cation seed, and n represents 2 or 3, and is characterized by reacting a tetrakis(fluoroaryl)borate compound obtained by any of the purifying processes 1-4 with a compound generating monovalent cation seeds.
According to the above process, an inexpensive tetrakis(fluoroaryl)borate derivative can be produced efficiently from the tetrakis(fluoroaryl)borate compound obtained through any of the above purifying processes, namely, alkali metal salts, alkaline earth metal salts, and hydrides of tetrakis(fluoroaryl)borate. The resulting tetrakis(fluoroaryl)borate derivative does not contain the impurities, such as magnesium halide, and therefore is so pure that it can be used suitably as, for example, a co-catalyst of the metallocene catalyst used in the cationic complex polymerization reaction or photopolymeric catalyst for silicone.
Also, to fulfill the third object, the inventors of the present invention conducted an assiduous study on the tetrakis(fluoroaryl)borate ether complex and the producing process of the same. In due course, the inventors discovered that an inexpensive and highly-pure tetrakis(fluoroaryl)borate ether complex as a new material, which can be suitably used as an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds, can be obtained at high yield by reacting tetrakis(fluoroaryl)borate with a particular kind of ether compound.
In addition, the inventors achieved the present invention when they also discovered that even when tetrakis(fluoroaryl)borate.magnesium halide containing a coloring component derived from the Grignard reaction and by-product salts, such as magnesium bromide fluoride (MgBrF) produced as a by-product in the Grignard reaction, is used as a raw material, that is, tetrakis(fluoroaryl)borate, a tetrakis(fluoroaryl)borate ether complex can be obtained in the form of highly-pure crystals, from which the coloring component and by-product salts can be readily separated/removed.
In other words, a producing process of a tetrakis(fluoroaryl)borate ether complex of the present invention relates to a producing process of a tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4): ##STR4##
where each of R.sub.1 -R.sub.10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R.sub.1 -R.sub.5 represents a fluorine atom and at least one of R.sub.6 -R.sub.10 represents a fluorine atom, each of R.sub.11 and R.sub.12 represents a hydrocarbon group which may include a substituent group containing a hetero atom, Y represents a hydrocarbon bivalent group, M represents a hydrogen atom, alkali metal, alkaline earth metal, or alkaline earth metal halide, n represents 2 or 3, and m represents 1 when M represents a hydrogen atom, alkali metal, or alkaline earth metal halide, and 2 when M represents alkali earth metal, and is characterized by reacting tetrakis(fluoroaryl)borate expressed by General Formula (5): ##STR5##
where each of R.sub.1 -R.sub.10 represents a hydrogen atom, a fluorine atom, a hydrocarbon group, or an alkoxy group, provided that at least one of R.sub.1 -R.sub.5 represents a fluorine atom and at least one of R.sub.6 -R.sub.10 represents a fluorine atom, M represents a hydrogen atom, alkali metal, alkaline earth metal, or alkaline earth metal halide, n represents 2 or 3, and m represents 1 when M represents a hydrogen atom, alkali metal, or alkaline earth metal halide, and 2 when M represents alkali earth metal,
According to the above process, an inexpensive and highly-pure tetrakis(fluoroaryl)borate ether complex as a new material suitably used as, for example, a co-catalyst of the metallocene catalyst, a cationic polymerization initiator, or an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds, can be produced at high yield.
Also, according to the above process, even when a raw material, that is, tetrakis(fluoroaryl)borate, contains the impurities, a highly-pure tetrakis(fluoroaryl)borate ether complex from which the impurities are removed can be obtained. The tetrakis(fluoroaryl)borate ether complex obtained through the above process is so pure that it can be used suitably as, for example, a co-catalyst of the metallocene catalyst, a cationic polymerization initiator, or an intermediate for producing the tetrakis(fluoroaryl)borate derivatives of various kinds.
Further, to fulfill the fourth through seventh objects, the inventors of the present invention conducted an assiduous study. In due course, the inventors achieved the present invention when they discovered that an inexpensive and highly-pure tetrakis(fluoroaryl)borate derivative can be produced efficiently when both a particular kind of tetrakis(fluoroaryl)borate ether complex and a compound generating monovalent cation seeds are used as a starting material.
In other words, to fulfill the above objects, a producing process of the tetrakis(fluoroaryl)borate derivative of the present invention expressed by General Formula (2) above is characterized by using both the tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4) above and a compound generating monovalent cation seeds as a starting material.
According to the above process, since the tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4) above, which can be readily and highly purified compared with tetrakis(fluoroaryl)borate, is used as the starting material, the tetrakis(fluoroaryl)borate derivative expressed by General Formula (2) above can be produced efficiently with high purity at low costs.
In addition, to fulfill the above objects, a producing process of tetrakis(fluoroaryl)borate expressed by General Formula (5) above is characterized by removing the ether compound expressed by General Formula (6) above from the tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4) above.
According to the above processes, since the tetrakis(fluoroaryl)borate ether complex expressed by General Formula (4) above, which can be readily and highly purified compared with tetrakis(fluoroaryl)borate, borate ether complex expressed by General Formula (4) above with a compound generating monovalent cation seeds.
According to the above process, the tetrakis(fluoroaryl)borate derivative.ether complex expressed as General Formula (7) above as a new, useful material for an intermediate in producing the tetrakis(fluoroaryl)borate derivative can be produced.
Further, to fulfill the above objects, a producing process of the tetrakis(fluoroaryl)borate derivative of the present invention expressed by General Formula (2) above is characterized by removing the ether compound expressed by General Formula (6) above from the tetrakis(fluoroaryl)borate derivative.ether complex expressed by General Formula (7) above.
According to the above process, the tetrakis(fluoroaryl)borate derivative expressed by General Formula (2) above can be produced from the tetrakis(fluoroaryl)borate derivative.ether complex expressed by General Formula (7) above efficiently at low costs.